CN105419261A - Biodegradable material, preparation method and applications thereof - Google Patents
Biodegradable material, preparation method and applications thereof Download PDFInfo
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- CN105419261A CN105419261A CN201410408055.6A CN201410408055A CN105419261A CN 105419261 A CN105419261 A CN 105419261A CN 201410408055 A CN201410408055 A CN 201410408055A CN 105419261 A CN105419261 A CN 105419261A
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Abstract
The present invention provides a biodegradable material, which is prepared from the following raw materials by weight: 10-35% of a 3-hydroxybutyric acid and 4-hydroxybutyric acid copolymer, 10-35% of polybutylene succinate, 0-50% of polylactic acid, 5-25% of vegetable oil, 1-10% of a plasticizer, and 0.02-5% of a reaction accelerating agent. The present invention further provides a preparation method of the biodegradable material, and applications of the biodegradable material in preparation of biodegradable films. According to the present invention, the biodegradable material is a degradable biological material, has characteristics of excellent elongation at break, excellent tensile strength, good transparency, and excellent comprehensive performance; the method has characteristics of simple process, easy control, strong operability, and low production cost; and after the biodegradable material is simply processed, the biodegradable film can be obtained, and advantages of easy industrial production, good economic benefits and broad application prospects are provided.
Description
Technical field
The present invention relates to the composition of macromolecular compound, be specifically related to a kind of biodegradable material, and the preparation method and application of this biodegradable material.
Background technology
Since the thirties in 20th century, plastic material came into operation, with bright and clean attractive in appearance, corrosion-resistant, the excellent properties such as production technique is simple of its light weight, inexpensive, appearance, each department of national economy and each field of people's lives are widely used in.Due to the extensive application of plastics, scrapped plastic products grows with each passing day, and the most stable performance of plastics, therefore there is so-called white pollution, bring very large harm to environment.In recent years, the improvement of people to waste plastic takes positive measure, and such as, the minimizing of Plastic Packaging Materials, repeatedly uses, and recycling etc.But, those are not easily reclaimed, recovery value is little or recycle the goods being difficult to economically run, as shopping bag, disposable tableware, agricultural mulching, medical plastic ware etc., adopt degradative plastics to make then advantageously.
But degradative plastics is the more late material grown up, be also in a growth, perfect stage at present.Although existing degradative plastics has biodegradability, be conducive to environment protection, mostly can not keep the good transparency, and/or mechanical property be not good, made goods particularly film based article are easily damaged.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of biodegradable material, and the preparation method and application of this biodegradable material, this biodegradable material not only has biological degradability, and has excellent mechanical property, and keeps the transparency preferably.The technical scheme adopted is as follows:
A kind of biodegradable material, is characterized in that being made up of the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 ~ 35%;
Poly butylene succinate 10 ~ 35%;
Poly(lactic acid) 0 ~ 50%;
Vegetables oil 5 ~ 25%;
Softening agent 1 ~ 10%;
Reaction promotor 0.02 ~ 5%.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, vegetables oil, softening agent and reaction promotor are combined, and embody good elongation at break and good tensile strength, overall mechanics better performances.
Preferred above-mentioned biodegradable material is made up of the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 22%;
Poly butylene succinate 15 ~ 22%;
Poly(lactic acid) 25 ~ 50%; Vegetables oil 14 ~ 25%;
Softening agent 5 ~ 10%;
Reaction promotor 1 ~ 5%.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and the reaction promotor of above-mentioned weight proportion are combined, and embody good elongation at break and excellent tensile strength, excellent combination property.
Further preferred above-mentioned biodegradable material is made up of the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 19%;
Poly butylene succinate 15 ~ 19%;
Poly(lactic acid) 37 ~ 50%;
Vegetables oil 14 ~ 18%;
Softening agent 5 ~ 7%;
Reaction promotor 1 ~ 2%.
3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and the reaction promotor of above-mentioned weight proportion are combined, there is good elongation at break and very excellent tensile strength, be very suitable for making the goods such as plastic shopping bag.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate can improve the elongation at break of biodegradable material of the present invention.
Above-mentioned poly(lactic acid) can adopt L-type poly(lactic acid), D type poly(lactic acid) or LD mixed type poly(lactic acid).Poly(lactic acid) can improve the intensity of biodegradable material of the present invention.
Preferred above-mentioned vegetables oil is a kind of or wherein multiple combination in rapeseed oil, Viscotrol C, soybean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil and tung oil.Add vegetables oil, by the interaction of the active function groups in the reaction active groups in vegetables oil and matrix resin (i.e. 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate), to reach increase-volume object.
Above-mentioned softening agent is a kind of or wherein multiple combination in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid and glycerine.Add softening agent, the travelling performance of polymer chain can be improved, the plastic effect of biodegradable material is improved, reduce the fragility of biodegradable material, improve the flexibility of biodegradable material.
Preferred above-mentioned reaction promotor is a kind of in coupling agent and catalyzer or both combinations.
Preferred above-mentioned coupling agent is a kind of in silane compound and isocyanate compound or both combinations.As preferably, above-mentioned coupling agent is that γ-aminopropyl triethoxysilane (KH-550), diphenylmethanediisocyanate (MDI) and poly-methyl are to a kind of or wherein multiple combination in phenylisocyanate (being called for short PMDI).
Preferred above-mentioned catalyzer is a kind of in organic acid and inorganic proton acid or both combinations.As preferably, above-mentioned catalyzer is a kind of or wherein multiple combination in citric acid, hexanodioic acid, succinic acid and hydrochloric acid.
Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent, reaction promotor (comprising coupling agent, catalyzer) all can commercially buy, and wherein 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer can choose P (3HB-co-4HB) copolyesters that Tianjin Green Biomaterial Co., Ltd. produces.
The present invention also provides a kind of preparation method of above-mentioned biodegradable material, it is characterized in that comprising the steps: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor to mix, obtain mixture; Then mixture is joined melt blending in twin screw extruder, form material melt; Material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, and obtains material particles; After the process of material particles drying, obtain biodegradable material.The screw slenderness ratio of preferred twin screw extruder is 35 ~ 45:1, and the temperature of melt blending is 140 ~ 175 DEG C.Above-mentioned tie rod, pelletizing belong to the agglomeration technique means of existing routine.Above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate use last as need first to carry out drying treatment.
Above-mentioned biodegradable material is preparing the application in Biodegradable film, by described biodegradable material through singe screw inflation film manufacturing machine blown film, obtains Biodegradable film.The screw slenderness ratio of above-mentioned singe screw inflation film manufacturing machine is 25 ~ 35:1.Because above-mentioned biodegradable material has excellent elongation at break and tensile strength, and maintain the good transparency, be thus particularly suitable for manufacturing Biodegradable film.
The present invention compared with prior art, has following beneficial effect:
In biodegradable material of the present invention, main ingredient 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, vegetables oil and poly(lactic acid), all can be decomposed by the microorganisms under given conditions, belongs to Wholly-degradable biomaterial.In addition, 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), softening agent and reaction promotor are combined, can interact, there is certain synergy, biodegradable material of the present invention is made to embody excellent elongation at break and tensile strength, and maintain the good transparency, excellent combination property.
Preparation method's technique of biodegradable material of the present invention is simple, is easy to control, workable, low production cost; And by biodegradable material again after simple processing, just can obtain Biodegradable film, be easy to suitability for industrialized production and there is good economic benefit, having broad application prospects.
Biodegradable material of the present invention is highly suitable for preparing Biodegradable film, and the Biodegradable film made has very high intensity; The shopping bag made of this Biodegradable film can repeatedly Reusability, and still can use as refuse bag after a number of uses, and decomposed quick absorption completely by the microorganism in soil after discarded, environmental pollution is little, has good environmental benefit.
Embodiment
Embodiment 1
First, take the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 18 weight part, poly butylene succinate 17 weight part, poly(lactic acid) 42 weight part, vegetables oil 16 weight part (being Viscotrol C), softening agent 6 weight part (being polyoxyethylene glycol), reaction promotor 1 weight part (being diphenylmethanediisocyanate).First drying treatment is carried out before above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate use.
Then, prepare full-biodegradable material according to the following steps: mixed by above-mentioned all raw materials and (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 DEG C, the rotating speed of premixing machine is 800 ~ 1200 revs/min, mix 30 minutes, mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in twin screw extruder (each melt blending that mixture is respectively 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 175 DEG C, 165 DEG C, 160 DEG C, 150 DEG C through excess temperature is successively interval), form material melt; After material melt is extruded from the die head of twin screw extruder _ _ carry out tie rod, pelletizing, obtain material particles; After the process of material particles drying, obtain biodegradable material.The screw slenderness ratio of twin screw extruder is 40:1.Above-mentioned tie rod, pelletizing belong to the agglomeration technique means of existing routine, are not described in more detail at this.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and European Union EN13432 degraded standard.
By above-mentioned biodegradable material through singe screw inflation film manufacturing machine blown film, obtain Biodegradable film.The screw slenderness ratio of singe screw inflation film manufacturing machine is 25:1.
Embodiment 2
First, take the raw material of following weight part: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 weight part, poly butylene succinate 15 weight part, poly(lactic acid) 50 weight part, vegetables oil 14 weight part (being Viscotrol C), softening agent 5 weight part (being polyoxyethylene glycol), reaction promotor 1 weight part (being γ-aminopropyl triethoxysilane).First drying treatment is carried out before above-mentioned 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer and poly butylene succinate use.
Then, prepare full-biodegradable material according to the following steps: mixed by above-mentioned all raw materials and (all raw materials can be carried out pre-mixing in premixing machine, the initial temperature of mixing is 40 DEG C, the rotating speed of premixing machine is 800 ~ 1200 revs/min, mix 30 minutes, mixing process medium speed can improve gradually), obtain mixture; Then mixture is joined melt blending in twin screw extruder (each melt blending that mixture is respectively 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 175 DEG C, 165 DEG C, 160 DEG C, 150 DEG C through excess temperature is successively interval), form material melt; Material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, and obtains material particles; After the process of material particles drying, obtain biodegradable material.The screw slenderness ratio of twin screw extruder is 40:1.
Above-mentioned biodegradable material can meet U.S. ASTMD6400 and European Union EN13432 degraded standard.
By above-mentioned biodegradable material through singe screw inflation film manufacturing machine blown film, obtain Biodegradable film.The screw slenderness ratio of singe screw inflation film manufacturing machine is 25:1.
Claims (10)
1. a biodegradable material, is characterized in that being made up of the raw material of following weight per-cent:
3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 10 ~ 35%;
Poly butylene succinate 10 ~ 35%;
Poly(lactic acid) 0 ~ 50%;
Vegetables oil 5 ~ 25%;
Softening agent 1 ~ 10%;
Reaction promotor 0.02 ~ 5%.
2. biodegradable material according to claim 1, is characterized in that being made up of the raw material of following weight per-cent: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 22%;
Poly butylene succinate 15 ~ 22%;
Poly(lactic acid) 25 ~ 50%;
Vegetables oil 14 ~ 25%;
Softening agent 5 ~ 10%;
Reaction promotor 1 ~ 5%.
3. biodegradable material according to claim 2, is characterized in that being made up of the raw material of following weight per-cent: 3-hydroxybutyrate and 4 hydroxybutyric acid copolymer 15 ~ 19%;
Poly butylene succinate 15 ~ 19%;
Poly(lactic acid) 37 ~ 50%;
Vegetables oil 14 ~ 18%;
Softening agent 5 ~ 7%;
Reaction promotor 1 ~ 2%.
4. the biodegradable material according to any one of claim 1-3, is characterized in that: described vegetables oil is a kind of or wherein multiple combination in rapeseed oil, Viscotrol C, soybean oil, peanut oil, Oleum Cocois, plam oil, oleum lini, Oleum Gossypii semen, Semen Maydis oil, sunflower seed oil, pine-seed oil and tung oil.
5. the biodegradable material according to any one of claim 1-3, is characterized in that: described softening agent is a kind of or wherein multiple combination in sorbyl alcohol, polyoxyethylene glycol, acetylize citric acid and glycerine.
6. the biodegradable material according to any one of claim 1-3, is characterized in that: described reaction promotor is a kind of in coupling agent and catalyzer or both combinations.
7. biodegradable material according to claim 6, is characterized in that: described coupling agent is that γ-aminopropyl triethoxysilane, diphenylmethanediisocyanate and poly-methyl are to a kind of or wherein multiple combination in phenylisocyanate.
8. biodegradable material according to claim 6, is characterized in that: described catalyzer is a kind of or wherein multiple combination in citric acid, hexanodioic acid, succinic acid and hydrochloric acid.
9. the preparation method of biodegradable material according to claim 1, it is characterized in that comprising the steps: 3-hydroxybutyrate and 4 hydroxybutyric acid multipolymer, poly butylene succinate, poly(lactic acid), vegetables oil, softening agent and reaction promotor to mix, obtain mixture; Then mixture is joined melt blending in twin screw extruder, form material melt; Material melt carries out tie rod, pelletizing after the die head of twin screw extruder is extruded, and obtains material particles; After the process of material particles drying, obtain biodegradable material.
10. biodegradable material according to claim 1 is preparing the application in Biodegradable film, by described biodegradable material through singe screw inflation film manufacturing machine blown film, obtains Biodegradable film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410408055.6A CN105419261A (en) | 2014-08-19 | 2014-08-19 | Biodegradable material, preparation method and applications thereof |
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| CN201410408055.6A CN105419261A (en) | 2014-08-19 | 2014-08-19 | Biodegradable material, preparation method and applications thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083028A (en) * | 2017-05-19 | 2017-08-22 | 刘文军 | A kind of biodegradation material and preparation method thereof |
| CN107815075A (en) * | 2017-11-15 | 2018-03-20 | 广西塔锡科技有限公司 | A kind of biomass degradation material and preparation method thereof |
| CN110591311A (en) * | 2019-09-06 | 2019-12-20 | 淮安森辉智能科技有限公司 | Biodegradable plastic film and preparation method thereof |
| CN115926400A (en) * | 2023-01-03 | 2023-04-07 | 深圳市鼎力盛科技有限公司 | New material environment-friendly calabash film, preparation method and application thereof |
-
2014
- 2014-08-19 CN CN201410408055.6A patent/CN105419261A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083028A (en) * | 2017-05-19 | 2017-08-22 | 刘文军 | A kind of biodegradation material and preparation method thereof |
| CN107815075A (en) * | 2017-11-15 | 2018-03-20 | 广西塔锡科技有限公司 | A kind of biomass degradation material and preparation method thereof |
| CN110591311A (en) * | 2019-09-06 | 2019-12-20 | 淮安森辉智能科技有限公司 | Biodegradable plastic film and preparation method thereof |
| CN115926400A (en) * | 2023-01-03 | 2023-04-07 | 深圳市鼎力盛科技有限公司 | New material environment-friendly calabash film, preparation method and application thereof |
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